And cleveland



sheet 1.

2 Sheets I 11,. H. DOW. 1 .Assignor to the MIDLAND CHEMICAL COMPANY.

PROCESS OF EXTRAGTINGBROMINE.

No. 11,232. Reissr -ed Apr. 12, 1892\- i 1 v{gig/anion 44: in eJJeJ fl 2 SheetsSheet 2.-

H. H. DOW. Assignorfno the MIDLAND CHEMICAL COMPANY. PROCESS OP EXTRAGTING BROMINE.

' Np. 1 1,232, Reissued Apr. 12, 1892.

' UNITED STATES PATENT?OFFICE- HERBERT n. DOW, OFWMIDLAND, MICHIGAN, ASSIGNQRf-IO run MIDLAND CHEMICAL COMPANY, OF- MIDLAND,

MICHIGAN, 4 1 CLEVELAND, orno.

PROCESS OF EXTRACTING BRO MINE.

SPECIFICATION forming part of Reissued Letters Patent No. 11,232, dated April-12, 1892. i Original No. 460,370, dated September 29, 1891- Application for reissue filed March 14,1892. dSeri'al No. 424,938-

- full, clear, and exactdescription of the invention, suchas'will enable others skilled inthe 10 art to which it pertains tomakea'nd usethe I same. g

My invention relates to a new process of extracting bromine'from natural brine or from bitter water, as the case may be;-andit con-- r5 sists in the-steps hereinafter described andclaimed; Many salt-wells will not pay for working salt, owing to the low price of the latter commodity. The brine from some of these wells is rich in bromine, and it is a matactor of much commercial value to be able to cheaply recover the brominefrom the brine without incurring the expense of evaporating the water of the .brine; and myimproved process-has this end in view, although the process 2 5 is equally well adapted to working bitter waters where the brine has been worked for salt.

My process, in brief, consists, first, in setting the bromine free from its chemical combinations inthe brine, and this may be done by various means-401' example, by clectrie ity, or by the agency of chlorine gas, or by introducing into thebrine the equivalents of chlorine gas, to wit: first introducing sulphuric acid, followed by the ordinary bleach- 35, ingepowder of commerce. By means either of electricity, chlorine g'as,"or of the aforesaid chemicals the bromine is set fre eifromitschemicalcombinations,leavingthebrominein solntioninithe brine; second, the bromine is 0 recovered from its soluble condition in the brine, by means of air-currents brought in Contact with .the brine, the brominfebeing absorbed and carried away by .the "air," and subsequently the bromide is recovered from the 5 air by bringing such bromine laden air in contact with such substance as willreadily form a chemical combination with the bromine; For instance, bypassing such bromine-laden air through a body of iron-turn" 5o ings the bromine and iron will-chemically unite, forming bromide of iron, known as fership the bromine in solid condition it may be convertedinto ferrous bromide, which is a more staple compound when heated than the ferric bromide, by bringing the aforesaid solution in contact with iron, and subsequently evaporating it to dryness in a vessel from whichthe'air is excluded by steam or by other means, the product being a. solid, (FeBr,.) In place of the-ironturnings aforesaid for recovering the bromine from the air by substituting othermetals or substance having an afiinity for the bromine, other compounds of bromine may be had' such,.forinstance, as bromide of zinc, bromide of coppencal- 7o cium bromide and bromate, sodium bromide and bromate, 850. Also, other aeriform bodies other than atmospheric airmay be used for recoveringthe bromine from the brine-for instance, natnralor artificial gaswhere these may be had at small cost; but this must not be confounded with the use of chlorine gas in the first stages of the process for setting the bromine free from the chemical combination in the brine. i 1n the accompanyingdrawingsis illustrated suitable apparatus for carrying out my invention, although such'apparatus may be varied almost indefinitely. Figure 1 is an end elevation insection. Fig. 2 is an elevation in transverse sect-ion, taken through the center. of the apparatus employed in thelatter stages of the process.

A are storage-tanks for the brine and in which the brine is treated by electricity or ,with chlorine gas or by chemicals that are substantiallythe equivalentsof chlorine gasfor instancegsulphuric acid and common bleaching-powderfor freeing the bromine from its chemical combinations in the brine, 5 and this is usually done in one storage-tank -=at;a time. After such treatment the brine is drawn on into a shallow tank B, and during the drawing oif of the one storage-tank probably thebrine in another storage-tank too will be undergoing the treatment just referred to. Meanwhile possiblya third tank is filled with brine, so that the process may becontinu ous. Tank B is preferably located in aelosed room C, near the upper portion thereof, this tank 8 having a series of drip-holes, from- '5 which the brineis showered down, preferably upon sheets of burlap stretched upon frames in theinclined-position shown. In place of J burlap wooden surfaces may be employed; but. the burlap is preferable on account of the- 10 greater surface exposed to the air. 2

D is'ablower for furnishing the-airthat iscirculated through room 0-, the discharge-pipe D of this blower entering, as shown,n-ear'the bottom of room C,this airpassing upthrough a perforated fioo'r -G. The'air on entering the room from below first engages brine that has been nearly depleted of bromine, and the fresh airabsorbs this remnant of bromine al most to thelast degree. As the air passes upward it comes in contact with brine richer with-bromine, andat last comes in'c'ontact with the. brine that is' showered down, containing its full amo'untof bromine, and hence the'air in passing 0E through opening C has been laden with bromine to its run extent. The air passes elf through duct (1 and is conducted through the bottom of container E, this container being partially filled, for instance, with iron-turnings, or scrap-iron, in which case the'bromine uniting with the iron will-form bromide of iron, known 'as"ferri c bromide, and simultaneously therewith the moisture of the atmosphere will be absorbed by. the ferric bromideforming a solution,and 5 this ferric-bromidesolution dripsdownand is discharged through spout e into vessel F, the latter being preferably-jot stone. Vessel E is covered and the exhaust-pipe of the blower connects with this vessel. Hence the 0 air of the vessel after passing the iron and having been freed frornthe bromine is again returned to the bottom of room 0, and so theprocess goes on. In case other than atmos pheric air is used'such,'forinstance, as nat- 4'5 ural or artificial gas-the operation is the same. The lower fioor of the room is shown inclined, withthe discharging-spout G in the form of a trap for drawingpif the waste brine without wasting the 'air.'; If, in placeofiromfother -'si-i'bs-tanc'e having a strong affinity for bromine'be' introduced into vessel E, other f'compounds of bromine will of course be formed. p

The specific compound-of bromine that is 5 'formed is of secondary importance, the main' object being to get the bromine in some concentrated form, from which by subsequent arts can be made. i

For reducing the ferric-bromide solution. aforesaid i0 ferrous bromide the liquid from I container F is poured into towerL, the latter being filled with iron-turnings, scrap, or iro n flates .iihrgngh an the air previous to the introduction of the fer- -sisting,-first, in freeing'the bromine from its 1. -able absorbing materia processes 'the various-bromides used in the 'in some form. The tower terminates in' a .tube Z,.dis charging into vessel H. 'This-ve's- 5 sol-has asteam-jacltet H for heating the-vessel, and hasaremovablecoverH togetherwith the usual appliances-for hermetically sealing the vessel andsteam-jacket. A steam-pipe h leads into the steam-space of the jacket.- The 7c pipe h leads into vesselH near thetop of the latter, this latter pipe havin g a suitable 'check-- valve 7L2, that allows vapor to escape from the vcssel,lbntlprevents the ingress of air from theoutsidei: The1f rric bromide as it pereoorigin-tower L absorbs. 'mo'reircn, thusscon erting the-product into a ferrous bromide, this liquid being discharged -into vessel H,- 'the.1atter;being filled with an atmosphere of-steamproduced by-boiling a quantity of; water in the 've'ssehso as to expel rous bromide. This latter solution is boiled -to' dryness and afterward allowed tocooL- The cover of the vessel is then removed and 8 the solid product is taken out ofthe vessel, the-air having no decomposing effect onthe solid dry product. I

Iam aware of United States Letters Patent, Reissue No. 3,479, granted to Amalie Stieren June 1, 186 9 -but inthe process therein described for obtainiiig bromine there, is no mention of gasof'any kind, except chlorine gas, used for the purpose of freeing the bro mine from its chemical combination in the brine, and there is nothing said of employing atmospheric air or gas of any kind to recover the bromine thus set free,- and there is n othing in the patent that would even suggest the same.

What I claim is- 1 1. The-process herein described of cxtract- KOO ' iug bromine from brine or bitter wafer and reducing the productto a'solidbromide, con- 5. chem cal co mbrnation; second, separating the bromine from the brine by means of an airblast; third, "forcing the bromine-laden air through a metal or substance that will combine with the bromine, thus producing abro: mide, and, finally, boiling the latter to dryness out of contact with the air, substantially as set forth. 2. The improvement in the art of obtaining bromine from natural salt-water, which conmine free from its chemical combination, then absorbing the bromine from the air with suitr 20 .Initestirnony whereof I sign this specification,-in the presence of two. witnesses, this 9th day-of February, 1892.

4 HERBERT H, DOW. f Witnesses:

C. H. Donna, WAR HOOVER.

I I sists in-trea-ting such salt-water to set the bro- 

